Hard contact lens material and hard contact lens

Abstract

[Problem] To provide: a hard contact lens that has high oxygen permeability and, as a result of having a large bending deformation amount, is not easily damaged by bending deformation; and a hard contact lens material with which it is possible to manufacture the hard contact lens. [Solution] One aspect of the present invention provides a hard contact lens material which comprises a substituted methacrylate (A) having a molecular structure where the ratio of the number of fluorine atoms to the number of carbon atoms is 0.6-0.9, a substituted styrene (B), a methacryloyl group-containing silicone monomer (C), a (meth)acryloyl group-containing monomer (D), an unsaturated double bond-containing hydrophilic monomer (E), and a methacryloyl group-containing monomer (F), and in which the mole ratio of the (meth)acryloyl group-containing monomer (D) to the methacryloyl group-containing monomer (F) is 0.12-0.2.

Description

Hard contact lens materials and hard contact lenses

[0001] This invention relates to hard contact lens materials and hard contact lenses.

[0002] Contact lenses used for refractive correction are classified into soft contact lenses and hard contact lenses. Soft contact lenses, which are made of flexible materials and offer superior comfort, have a higher market share than hard contact lenses. However, hard contact lenses have advantages such as higher visual quality, superior astigmatism correction, and a tendency to make it easier to detect eye problems, due to their rigid material. Recently, hard contact lenses with special shapes are also being used as orthokeratology lenses, which are worn during sleep to change the shape of the cornea and correct nearsightedness and astigmatism.

[0003] Most hard contact lenses are conventional types used in a cycle of "insertion," "removal," "cleaning," and "storage." Therefore, to prevent eye problems, it is necessary to remove any dirt that accumulates during insertion, and thus daily cleaning by rubbing is important. To clean hard contact lenses by rubbing, apply a cleaning solution to the lens surface, rub it with your palm or fingertips, and then rinse with tap water or a special rinsing solution. However, if excessive force is applied in a direction that causes the lens to bend, the lens can easily break.

[0004] In particular, with hard contact lenses that have high oxygen permeability, the material itself is soft, making the lens surface prone to scratches during handling and rubbing, thus increasing the rate of breakage. Therefore, there is a need to develop hard contact lenses that have high oxygen permeability and a large amount of bending deformation when the lens is bent, making them less prone to breakage. As such a hard contact lens, for example, a contact lens using poly(organosiloxane) monomer and neopentyl glycol dimethacrylate as crosslinking monomers has been proposed (see Patent Document 1). Although this contact lens is said to have improved physical properties, its oxygen permeability is not sufficient, and the amount of bending deformation in the direction in which the lens bends is also not sufficient.

[0005] Furthermore, ophthalmic lens materials have been proposed that include silicone monomers having a styrene structure, fluorine-containing monomers, and crosslinkable monomers having vinyl groups and methacryloyl groups in their molecular structure (see Patent Document 2). However, although these ophthalmic lens materials have high oxygen permeability and impact strength (strength when a load is applied to one point of the lens), the lens breaks with small amounts of deformation, so it is difficult to say that the amount of bending deformation is sufficient.

[0006] JP-A-63-258917 JP-A-2-196809

[0007] In view of the above circumstances, the present invention aims to provide a hard contact lens that has high oxygen permeability and a large amount of bending deformation, making it resistant to damage from bending deformation, and a hard contact lens material that can be used to manufacture such a hard contact lens.

[0008] According to one aspect of the present invention, a hard contact lens material comprising: 35 mol% to 55 mol% of a fluoroalkyl methacrylate (A) having a molecular structure in which the ratio of the number of fluorine atoms to the number of carbon atoms is 0.6 or more and 0.9 or less; 4 mol% to 15 mol% of styrene (B) having a silicon-containing group; and 10 mol% to 30 mol% of at least one silicone monomer (C) having a methacryloyl group represented by the following general formula (I). [Z is one selected from a direct bond, the following linking structure (I-1), and the following linking structure (I-2), and R , ８ , , ５ , ６ , ３ , , ２ , １０ , ９ ,

[0009] , ７ ,

[0010] , ５ , , ４ , １ , １ , R ２ , R ３ and R ４ are each independently an alkyl group having from 1 to 4 carbon atoms, a is an integer of 1 or more and 3 or less, and n is 2 or 3. ] The glass transition temperature of the homopolymer is -30 ° C or lower, and at least one selected from the monomer (D) having two (meth) acryloyl groups in the molecular structure represented by the following general formulas (II) to (IV) is 0.6 mol% or more and 1.6 mol% or less, and [In the formula, X is a methyl group or a hydrogen atom, and R ５ , R ６ , R ７ , R ８ , R ９ and R １０ are each independently an alkyl group having from 1 to 6 carbon atoms, n １ is 3 or 4, and n ２ is an integer of 12 or more and 40 or less. ] [In the formula, X １ is a methyl group or a hydrogen atom, and n ３ is an integer of 12 or more and 30 or less. ] [In the formula, n ４ is an integer of 4 or more and 15 or less, and n ５ is an integer of 6 or more and 20 or less. ] A hydrophilic monomer (E) having one unsaturated double bond in the molecular structure is 18 mol% or more and 25 mol% or less, and a hard contact lens material is provided that includes a homopolymer having a glass transition temperature of 190 ° C or higher and a monomer (F) having two methacryloyl groups in the molecular structure, and the molar ratio of the monomer (D) to the monomer (F) is 0.12 or more and 0.2 or less.

[0009] According to such an aspect, it is possible to provide a hard contact lens that has high oxygen permeability and a large amount of bending deformation, and is difficult to break with respect to bending deformation.

[0010] This figure shows a hard contact lens set in a mounting fixture for compression bending testing. This figure shows the hard contact lens compressed to a predetermined distance between the mounting fixtures.

[0011] The hard contact lens material and hard contact lenses will be described in detail below. <<Hard Contact Lens Material and Hard Contact Lenses>> The hard contact lens material is used to manufacture hard contact lenses. This hard contact lens material comprises fluoroalkyl methacrylate (A), styrene having a silicon-containing group (B), a silicone monomer containing a methacryloyl group (C), a monomer (D) having a homopolymer glass transition temperature of -30°C or lower and two (meth)acryloyl groups in its molecular structure, a hydrophilic monomer (E) having one unsaturated double bond in its molecular structure, and a monomer (F) having a homopolymer glass transition temperature of 190°C or higher and two methacryloyl groups in its molecular structure.

[0012] Hereinafter, fluoroalkyl methacrylate (A) will also be referred to as "substituted methacrylate (A)", styrene having a silicon-containing group (B) will also be referred to as "substituted styrene (B)", and silicone monomer containing a methacryloyl group (C) will also be referred to as "methacryloyl group-containing silicone monomer (C)". Furthermore, monomer (D) having two (meth)acryloyl groups in its molecular structure will also be referred to as "(meth)acryloyl group-containing monomer (D)", hydrophilic monomer (E) having one unsaturated double bond in its molecular structure will also be referred to as "unsaturated double bond-containing hydrophilic monomer (E)", and monomer (F) having two methacryloyl groups in its molecular structure will also be referred to as "methacryloyl group-containing monomer (F)".

[0013] The hard contact lens material is a monomer mixture containing a substituted methacrylate (A), a substituted styrene (B), a methacryloyl group-containing silicone monomer (C), a (meth)acryloyl group-containing monomer (D), an unsaturated double bond-containing hydrophilic monomer (E), and a methacryloyl group-containing monomer (F). Therefore, in the following, the hard contact lens material will also be referred to as the "monomer mixture." The monomer mixture may also contain any additives as needed, such as reactive monomers with UV absorption properties and colorants (see below). Each component will be described in turn below.

[0014] <Substituted Methacrylate (A)> Substituted methacrylate (A) is a component (fluorine-containing monomer) that is added to monomer mixtures for purposes such as imparting hardness and oxygen permeability to hard contact lenses (polymers of hard contact lens materials). There are many other fluorine-containing monomers besides substituted methacrylate (A), but substituted methacrylate (A) is preferred because it is readily available and can impart high oxygen permeability.

[0015] In such substituted methacrylate (A), a decrease in the number of fluorine atoms tends to reduce the oxygen permeability of the hard contact lens. On the other hand, an increase in the number of fluorine atoms inevitably results in a longer chain structure, making the resulting polymer of hard contact lens material softer and less processable. Therefore, there is an appropriate relationship between the number of carbon atoms and the number of fluorine atoms in the substituted methacrylate (A). Specifically, it is preferable that the ratio of the number of fluorine atoms to the number of carbon atoms in the molecular structure of the substituted methacrylate (A) is approximately 0.6 to 0.9 (i.e., the substituted methacrylate (A) has a molecular structure in which the ratio of the number of fluorine atoms to the number of carbon atoms is approximately 0.6 to 0.9), more preferably approximately 0.7 to 0.86, and even more preferably approximately 0.75 to 0.86. In this case, the oxygen permeability of the hard contact lens can be sufficiently high while maintaining good processability of the polymer of the hard contact lens material.

[0016] Examples of substituted methacrylates (A) include 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2,2,3,4,4,4-hexafluorobutyl methacrylate, 2-methyl-2,2,2-trifluoro-1-methyl-1-(trifluoromethyl)ethyl methacrylate, and 2,2,3,3,4,4,4-heptafluorobutyl methacrylate. These substituted methacrylates (A) may be used individually or in combination of two or more. Among these, it is preferable that substituted methacrylate (A) includes 1,1,1,3,3,3-hexafluoroisopropyl methacrylate.

[0017] The content of substituted methacrylate (A) in the hard contact lens material is approximately 35 mol% to 55 mol%, but preferably 35 mol% to 50 mol%, and more preferably 40 mol% to 50 mol%. In this case, the oxygen permeability of the hard contact lens and the processability of the hard contact lens material into a lens shape are improved, and a decrease in the amount of bending deformation of the hard contact lens can be prevented or suppressed.

[0018] In this specification, "mol%" means the total amount (100 mol%) of the number of moles of substituted methacrylate (A), the number of moles of substituted styrene (B), the number of moles of methacryloyl group-containing silicone monomer (C), the number of moles of (meth)acryloyl group-containing monomer (D), the number of moles of double bond-containing hydrophilic monomer (E), the number of moles of methacryloyl group-containing monomer (F), the number of moles of an optional UV-absorbing reactive monomer (G), the number of moles of colorant (H), and the number of moles of polymerization initiator (J), that is, the proportion (mol%) of a predetermined component to the entire hard contact lens material (100 mol%).

[0019] <Substituted Styrene (B)> Substituted styrene (B) is a component added to monomer mixtures for the purpose of providing hard contact lenses with high oxygen permeability and, incidentally, hardness. Substituted styrene (B) has a silicon-containing group, and by adjusting the number of silicon atoms in this silicon-containing group, it is possible to provide hard contact lenses with a good balance of oxygen permeability and hardness. Specifically, the number of silicon atoms in the silicon-containing group of substituted styrene (B) is preferably 4 to 6, more preferably 4 to 5, and even more preferably 4. In this case, the above effects can be further improved.

[0020] Examples of such substituted styrenes (B) include tris(trimethylsiloxy)silylstyrene, 1-(4-ethenylphenyl)-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane, 1-(4-ethenylphenyl)-1,1,5,5,5-pentamethyl-3,3-bis[(trimethylsilyl)oxy]trisiloxane, 3-(4-ethenylphenyl)-1,1,1,3,7,7,7-heptamethyl-5,5-bis[(trimethylsilyl)oxy]tetrasiloxane, and 3-(4-ethenylphenyl)-1,1,1,5,7,7,7-heptamethyl-3,5-bis[(trimethylsilyl)oxy]tetrasiloxane. These substituted styrenes (B) may be used individually or in combination of two or more. Among these, the substituted styrene (B) preferably includes tris(trimethylsiloxy)silylstyrene. The content of substituted styrene (B) in the hard contact lens material is approximately 4 mol% to 15 mol%, but is preferably approximately 4 mol% to 12 mol%, and more preferably approximately 4 mol% to 10 mol%. In this case, the oxygen permeability of the hard contact lens and the processability of the hard contact lens material into a lens shape are improved, and polymerization strain of the hard contact lens can be reduced, and a decrease in bending deformation can be prevented or suppressed.

[0021] <Methacryloyl Group-Containing Silicone Monomer (C)> Methacryloyl group-containing silicone monomer (C) is a component added to monomer mixtures for the purpose of supplementing oxygen permeability to hard contact lenses and improving the solubility of (meth)acryloyl group-containing monomer (D), which will be described later. This methacryloyl group-containing silicone monomer (C) is at least one compound represented by the following general formula (I). [Z is one of the following selected types: direct bond, linked structure (I-1), and linked structure (I-2), R １ , R ２ , R ３ and R ４ Each of these is an alkyl group having 1 to 4 carbon atoms, a is an integer between 1 and 3, and n is 2 or 3.

[0022] Specific examples of the methacryloyl group-containing silicone monomer (C) represented by this general formula (I) include, for example, 3-methacryloxypropyltris(trimethylsiloxy)silane, (3-methacryloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane, and methacryloxymethylphenethyltris(trimethylsiloxy)silane. The content of the methacryloyl group-containing silicone monomer (C) in the hard contact lens material is approximately 10 mol% to 30 mol%, more preferably 12 mol% to 25 mol%, and even more preferably 14 mol% to 25 mol%. In this case, it is possible to prevent a decrease in the processability of the hard contact lens material into a lens shape, while supplementarily improving the oxygen permeability of the hard contact lens and further improving the solubility of the (meth)acryloyl group-containing monomer (D) described later.

[0023] <(meth)acryloyl group-containing monomer (D)> (meth)acryloyl group-containing monomer (D) is a component added to monomer mixtures for purposes such as increasing the bending deformation of hard contact lenses. When a homopolymer is synthesized using (meth)acryloyl group-containing monomer (D), the glass transition temperature of the homopolymer is approximately -30°C or lower, preferably approximately -40°C or lower, and more preferably approximately -50°C or lower. The lower limit of the glass transition temperature of the homopolymer is not particularly limited, but is approximately -130°C. Therefore, the glass transition temperature of the homopolymer can be, for example, approximately -130°C or higher and -30°C or lower. Although the detailed mechanism is not clear, the inventors have found that by including (meth)acryloyl group-containing monomer (D) and methacryloyl group-containing monomer (F), described later, and by appropriately setting their molar ratio (blending ratio), the bending deformation of hard contact lenses can be increased.

[0024] This (meth)acryloyl group-containing monomer (D) is at least one selected from the compounds represented by the following general formulas (II) to (IV). [In the formula, X is a methyl group or a hydrogen atom, R ５ , R ６ , R ７ , R ８ , R ９ and R １０ Each of these is an alkyl group having 1 to 6 carbon atoms, and n １ is 3 or 4, and n ２ [This is an integer between 12 and 40, inclusive.]

[0025] In the above general formula (II), n ２It is preferable that the integer is between 12 and 38, more preferably between 15 and 30, and even more preferably between 18 and 28. In this case, it is possible to increase the amount of bending deformation of the hard contact lens while improving oxygen permeability. Furthermore, it is possible to prevent a decrease in the solubility of the component in the monomer mixture and a decrease in the processability of the hard contact lens material into a lens shape. It is preferable that urethane bonds or urea bonds, etc., are not included in the molecular structure of the compound represented by general formula (II) because they induce a decrease in the strength of the hard contact lens through hydrolysis and reduce the solubility of the fluorine-containing monomer which is the substituted methacrylate (A).

[0026] [In the formula, X １ is a methyl group or a hydrogen atom, n ３ n is an integer between 12 and 30. ] In the above general formula (III), n ３ It is preferably an integer between 12 and 28, more preferably an integer between 12 and 25, and even more preferably an integer between 14 and 25.

[0027] [In the formula, n ４ n is an integer between 4 and 15, and ５ n is an integer between 6 and 20. ] In the above general formula (IV), n ４ n is preferably an integer between 5 and 12, more preferably an integer between 5 and 10, and even more preferably an integer between 6 and 10. ５ It is preferably an integer between 8 and 20, more preferably an integer between 10 and 20, and even more preferably an integer between 12 and 20.

[0028] In the above general formulas (II) to (IV), n １ , n ２ , n ３ , n ４ and n ５ The values ​​of each may or may not have a distribution. １ , n２ , n ３ , n ４ and n ５ The statement that the values ​​of n do not have a distribution means, for example, １ When the value is 3, it means a single repeating number that does not include other values ​​(2, 4, etc.). Furthermore, in this specification, "average value" applies when there is a distribution in the repeating number in the dialkylsiloxane structure of general formula (II), the ethylene oxide group of general formula (III), the ethylene oxide group of general formula (IV), and the propylene oxide group. Specifically, the "average value" refers to the (meth)acryloyl group-containing monomer (D) １ This refers to the value obtained by performing 1H-NMR analysis, calculating the number of repeats using the peak integral intensity ratio of the dialkylsiloxane structure, ethylene oxide group, and propylene oxide group, and rounding the result to the first decimal place.

[0029] The compounds represented by the above general formulas (III) and (IV) have the function of increasing the bending deformation amount of hard contact lenses, as well as the function of supplementarily improving the water wettability of the surface of hard contact lenses. The content of (meth)acryloyl group-containing monomer (D) in the hard contact lens material is approximately 0.6 mol% to 1.6 mol%, but is preferably approximately 0.8 mol% to 1.4 mol%, and more preferably approximately 1 mol% to 1.4 mol%. In this specification, compounds with a molecular weight of less than 800 are also called "monomers," and compounds with a molecular weight of 800 or more are also called "macromonomers." In this specification, "(meth)acryloyl group" means either a methacryloyl group or an acryloyl group.

[0030] <Unsaturated Double Bond-Containing Hydrophilic Monomer (E)> Unsaturated double bond-containing hydrophilic monomer (E) is a component added to monomer mixtures for purposes such as improving the water wettability of the hard contact lens surface and improving the processability of the hard contact lens material into a lens shape. At least one of the following can be used as a component: unsaturated carboxylic acid, unsaturated amide, etc. Examples of unsaturated carboxylic acids include acrylic acid and methacrylic acid. Examples of unsaturated amides include acrylamide, methacrylamide, and N,N-dimethylacrylamide. The content of unsaturated double bond-containing hydrophilic monomer (E) in the hard contact lens material is approximately 18 mol% to 25 mol%, but is preferably 18 mol% to 24 mol%, and more preferably 20 mol% to 24 mol%. In this case, the water wettability of the hard contact lens surface and the processability of the hard contact lens material into a lens shape are improved, and a decrease in oxygen permeability and transparency of the hard contact lens can also be prevented.

[0031] <Methacryloyl Group-Containing Monomer (F)> Methacryloyl group-containing monomer (F) is a component added to monomer mixtures for purposes such as increasing the bending deformation of hard contact lenses and improving the processability of hard contact lens materials into lens shapes. When a homopolymer is synthesized using methacryloyl group-containing monomer (F), the glass transition temperature of the homopolymer is approximately 190°C or higher, preferably 195°C or higher, and more preferably 200°C or higher. The upper limit of the glass transition temperature of the homopolymer is not particularly limited, but is approximately 300°C. Therefore, the glass transition temperature of the homopolymer can be, for example, approximately 190°C to 300°C.

[0032] These components preferably do not contain urethane bonds or urea bonds in their molecular structure, from the viewpoint of preventing a decrease in the strength of hard contact lenses due to hydrolysis and a decrease in solubility in fluorine-containing monomers, which are substituted methacrylates (A). Examples of such methacryloyl group-containing monomers (F) include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, neopentyl glycol dimethacrylate, and the like.

[0033] The content of methacryloyl group-containing monomer (F) in the hard contact lens material is set in relation to the amount of (meth)acryloyl group-containing monomer (D) used. Specifically, the molar ratio of (meth)acryloyl group-containing monomer (D) to methacryloyl group-containing monomer (F) is approximately 0.12 to 0.2. Here, a molar ratio of approximately 0.12 to 0.2 means, for example, that when the amount of (meth)acryloyl group-containing monomer (D) used is 1.2 mol%, the amount of methacryloyl group-containing monomer (F) used is approximately 6 mol% to 10 mol%. Furthermore, the molar ratio of (meth)acryloyl group-containing monomer (D) to methacryloyl group-containing monomer (F) is preferably approximately 0.13 to 0.19, and more preferably approximately 0.14 to 0.18. In this case, the amount of bending deformation of the hard contact lens can be increased, and a decrease in the processability of the hard contact lens material into a lens shape, as well as deformation of the lens shape of the hard contact lens after rubbing and cleaning (for example, a change in the base curve), can be prevented or suppressed.

[0034] <Other Ingredients> • Reactive monomer (G) with UV absorption properties Reactive monomer (G) with UV absorption properties (hereinafter also simply referred to as "reactive monomer (G)") has a structure capable of absorbing ultraviolet light and is an optional ingredient that is added to monomer mixtures for purposes such as imparting ultraviolet absorption ability to hard contact lenses. Specific examples of reactive monomers (G) include, for example, 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole, 2-hydroxy-4-(methacryloyloxy)benzophenone, 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole, 2-(2-hydroxy-3-(methacryloxyaminomethyl)-5-tert-octylphenyl)-2H-benzotriazole, 2-[3'-tert-butyl-2'-hydroxy-5'-(3"-methacryloyloxypropyl)phenyl]-5-chlorobenzotriazole, and 2-[3'-tert-butyl-2'-hydroxy-5'-(3"-methacryloyloxypropoxy)phenyl]-5-methoxybenzotriazole.

[0035] Among these, the reactive monomer (G) is preferably 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole, 2-[3'-tert-butyl-2'-hydroxy-5'-(3"-methacryloyloxypropyl)phenyl]-5-chlorobenzotriazole, or 2-[3'-tert-butyl-2'-hydroxy-5'-(3"-methacryloyloxypropoxy)phenyl]-5-methoxybenzotriazole. These compounds may be used individually or in combination of two or more. The content of the reactive monomer (G) in the hard contact lens material is preferably about 0.6 mol% or less, and more preferably about 0.2 mol% to 0.5 mol%.

[0036] • Colorants (H) Colorants (H) are optional components added to monomer mixtures for purposes such as improving visibility by coloring hard contact lenses. These colorants (H) are classified into reactive colorants, which contain at least one unsaturated double bond in their molecular structure and chemically bond with the components that make up the hard contact lens, and non-reactive colorants, which do not contain an unsaturated double bond and whose colorant molecules are fixed within the three-dimensional network structure of the polymer that makes up the hard contact lens.

[0037] Reactive colorants that can be used include, for example, azo colorants, pyrazolone colorants, anthraquinone colorants, and cyanine colorants. Specific examples include, for instance, 1-(4-vinylbenzylamino)-4-phenylaminoanthraquinone, 1,4-bis(4-methylphenylamino)anthraquinone, 1,4-bis[4-(2-methacryloxyethyl)phenylamino]-9,10-anthraquinone, 1,5-bis((meth)acryloylamino)-9,10-anthraquinone, (meth)acryloylated tetraaminocopper phthalocyanine, and (meth)acryloylated (dodecanoylated tetraaminocopper phthalocyanine).

[0038] Specific examples of non-reactive colorants include, for example, Solvent Green 3, Solvent Green 7, Solvent Green 28, Solvent Yellow 18, Solvent Red 17, Solvent Red 23, Solvent Red 72, Solvent Blue 63, Solvent Violet 13, etc. The content of the colorant (H) in the hard contact lens material is preferably about 0.001 mol% or more and 0.01 mol% or less.

[0039] • Polymerization initiator (J) The polymerization initiator (J) can be either a thermal polymerization initiator or a photopolymerization initiator. Examples of thermal polymerization initiators include di(4-tert-butylcyclohexyl)peroxydicarbonate, di(3,5,5-trimethylhexanoyl)peroxide, dilauroyl peroxide, benzoyl peroxide, tert-hexylperoxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, 2,5-dimethyl-2, Examples include peroxides such as 5-bis(2-ethylhexanoylperoxy)hexane, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(isobutyronitrile), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), dimethyl-1,1'-azobis(1-cyclohexanecarboxylate), and 1,1'-azobis(cyclohexane-1-carbonitride).

[0040] Examples of photopolymerization initiators include benzoin methyl ether, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. The content of the polymerization initiator (J) in the hard contact lens material is appropriately selected depending on the polymerization temperature in thermal polymerization, the wavelength and intensity of light irradiation in photopolymerization, etc., but it is preferably about 0.1 mol% to 1 mol%.

[0041] <<Manufacturing Method for Hard Contact Lenses>> Hard contact lenses can be manufactured from the monomer mixture used as a hard contact lens material as described above. That is, the hard contact lenses of this embodiment include a polymer (cured product) of the hard contact lens material, or a processed product of this polymer. There are no restrictions on the manufacturing method of hard contact lenses, but for example, the following method can be used. First, the above components are homogeneously mixed to prepare a monomer mixture, which is then poured into a container made of a material such as metal, glass, or plastic. After that, the monomer mixture is polymerized by heat to produce a monomer mixture polymer of a predetermined shape (for example, rod-shaped, block-shaped, plate-shaped, etc.). It is preferable to complete this thermal polymerization continuously in a constant temperature bath at a temperature range of approximately 30°C to 50°C for approximately 72 hours to 200 hours.

[0042] After polymerization, it is preferable to perform a reheating treatment to further reduce the amount of unpolymerized monomers in the polymer. In this reheating treatment, first, the lid of the container in which polymerization has been completed is removed to open the container, and then the container with the polymer inside is placed in a heat treatment device. Next, the temperature is gradually increased in a range from room temperature to about 90°C or less, and the polymer is heated continuously for about 24 hours to 100 hours, after which it is cooled to room temperature. By performing this reheating treatment, it is possible to reduce the amount of unpolymerized monomers and oligomers remaining in the polymer.

[0043] During this reheating process, it is preferable to continuously supply (inflow) and discharge (outflow) a constant flow rate of air or nitrogen gas into the heat treatment device. This allows for efficient removal of unpolymerized monomers from the polymer. The higher the flow rate of the gas supplied into the heat treatment device, the more efficient the removal of unpolymerized monomers becomes, but a flow rate of approximately 10 L / min to 100 L / min is sufficient. After the reheating process, the polymer is removed from the polymerization container and then processed into the desired shape (for example, the shape of the hard contact lens itself) by cutting and polishing. This processing is called the lace-cut method.

[0044] Separately, hard contact lenses can also be manufactured by methods such as the cast molding method, in which a monomer mixture is injected into a mold having a predetermined curvature to directly form the lens shape. When this mold is used as a container, thermal polymerization can be carried out by placing the mold in a polymerization apparatus and gradually raising the temperature in a range of room temperature to about 90°C for about 10 to 72 hours, or by placing the mold in a polymerization apparatus set to a predetermined temperature (about 90°C or lower) and heating for about 1 to 48 hours. The atmosphere during thermal polymerization is preferably an inert gas atmosphere such as nitrogen or argon gas. By performing thermal polymerization in such an atmosphere, the polymerization rate of monomers can be improved and the amount of unpolymerized monomers can be reduced.

[0045] When polymerization is performed using light, the wavelength of the irradiated light is appropriately selected according to the characteristics of the photopolymerization initiator used, and is therefore not particularly limited. Specific examples of lamps used for light irradiation include, for example, lamps with strong peaks in the range of 200 nm to 280 nm and at 350 nm, lamps emphasizing wavelengths in the range of 350 nm to 400 nm, lamps emphasizing wavelengths in the range of 400 nm to 425 nm centered around 420 nm, and lamps emphasizing wavelengths in the range of 400 nm to 450 nm. The light irradiation intensity will vary depending on the light-receiving area of ​​the measuring instrument, but for example, 1 mW / cm² ２ 100mW / cm or more ２ It is preferable that it be within the following range.

[0046] The light irradiation time (polymerization time) is set appropriately according to the light irradiation intensity and is therefore not particularly limited. For example, if the light irradiation intensity is 1 mW / cm² ２ 100mW / cm or more ２If the following conditions are met, the irradiation time is preferably between 15 minutes and 120 minutes. In this photopolymerization, the atmosphere during polymerization is preferably an inert gas atmosphere such as nitrogen or argon gas, and the reheating treatment described above is preferable for the purpose of further reducing the amount of unpolymerized monomer in the polymer. The surface of the hard contact lens obtained in this way may be subjected to further treatments to improve water wettability, such as low-temperature plasma treatment or atmospheric pressure plasma treatment, as needed.

[0047] <<Hard Contact Lenses>> When measuring the amount of flexural deformation at the time of fracture of a hard contact lens (polymer of hard contact lens material) according to the test method described in ISO 18369-4:2017 (4.3 Rigid lens flexural deformation and fracture), it is preferably about 70% or more, more preferably about 72% or more, and even more preferably about 75% or more. There is no particular upper limit to the amount of flexural deformation at the time of fracture, but it is usually about 90%. Therefore, the amount of flexural deformation at the time of fracture can be, for example, between 70% and 90%. Hard contact lenses exhibiting such an amount of flexural deformation at the time of fracture can be judged to have excellent mechanical strength.

[0048] The amount of bending deformation at the time of fracture is a value that can be determined by the following formula. For example, "the amount of bending deformation at the time of fracture is 70%" means that when a hard contact lens with a diameter (initial diameter) of 9.5 mm is compressed at a test speed of 200 mm / min in a test environment of 23°C and 50% humidity, the distance between the mounting fixtures at the time of fracture of the hard contact lens is 2.85 mm (see Figures 1 and 2). [In the formula, "d" is the distance between the installation fixtures when the hard contact lens breaks, and "D Ｔ This is the initial diameter of the hard contact lens.

[0049] Furthermore, the oxygen permeability coefficient of hard contact lenses (polymers of hard contact lens materials) was measured according to the test method described in ISO 18369-4:2017 (4.4 Oxygen permeability, 4.4.3 Polarographic method), and was 120 × 10⁻¹⁰. －１１ (cm ２ / sec)・(mLO ２ It is preferable that the concentration be approximately 130 × 10 (mL × mmHg) or higher. －１１ (cm ２ / sec)・(mLO ２ It is more preferable that the concentration be approximately 140 × 10 (mL × mmHg) or higher. －１１ (cm ２ / sec)・(mLO ２ It is even more preferable that the oxygen permeability coefficient be approximately 200 × 10⁻¹⁰. The upper limit of the oxygen permeability coefficient is not particularly limited, but is usually 200 × 10⁻¹⁰. －１１ (cm ２ / sec)・(mLO ２ It is approximately (mL × mmHg). Therefore, the oxygen permeability coefficient is, for example, 120 × 10 －１１ (cm ２ / sec)・(mLO ２ / (mL × mmHg)) 200 × 10 －１１ (cm ２ / sec)・(mLO ２ The oxygen permeability coefficient can be set to approximately (mL × mmHg) or less. Hard contact lenses having such an oxygen permeability coefficient can be judged to have extremely high oxygen permeability.

[0050] Furthermore, the durometer hardness (Type D) of the hard contact lens (polymer of hard contact lens material), measured under a test environment of 23°C and 50% humidity, is preferably 74 to 78, more preferably 75 to 78, and even more preferably 76 to 78. A hard contact lens having such durometer hardness (Shore D hardness) can be judged to have excellent mechanical strength. Furthermore, it may be provided in the embodiments described below.

[0051] (1) A hard contact lens material comprising: 35 mol% to 55 mol% of fluoroalkyl methacrylate (A) having a molecular structure in which the ratio of the number of fluorine atoms to the number of carbon atoms is 0.6 or more and 0.9 or less; 4 mol% to 15 mol% of styrene (B) having a silicon-containing group; and 10 mol% to 30 mol% of at least one silicone monomer (C) having a methacryloyl group represented by the following general formula (I). [Z is one of the following selected types: direct bond, linked structure (I-1), and linked structure (I-2), R １ , R ２ , R ３ and R ４ Each of these is an alkyl group having 1 to 4 carbon atoms, a is an integer between 1 and 3, and n is 2 or 3. The homopolymer has a glass transition temperature of -30°C or lower, and contains at least one monomer (D) selected from those having two (meth)acryloyl groups in the molecular structure represented by the following general formulas (II) to (IV), in an amount of 0.6 mol% to 1.6 mol%, [In the formula, X is a methyl group or a hydrogen atom, R ５ , R ６ , R ７ , R ８ , R ９ and R １０ Each of these is an alkyl group having 1 to 6 carbon atoms, and n １ is 3 or 4, and n ２ [This is an integer between 12 and 40, inclusive.] [In the formula, X １ is a methyl group or a hydrogen atom, n ３ [This is an integer between 12 and 30, inclusive.] [In the formula, n ４ n is an integer between 4 and 15, and ５is an integer of 6 or more and 20 or less. A hydrophilic monomer (E) having one unsaturated double bond in the molecular structure is 18 mol% or more and 25 mol% or less, and the glass transition temperature of the homopolymer is 190 ° C or more. And a monomer (F) having two methacryloyl groups in the molecular structure, and the molar ratio of the monomer (D) to the monomer (F) is 0.12 or more and 0.2 or less. Hard contact lens material.

[0052] (2) In the hard contact lens material according to (1) above, the fluoroalkyl methacrylate (A) contains 1,1,1,3,3,3-hexafluoroisopropyl methacrylate. Hard contact lens material.

[0053] (3) In the hard contact lens material according to (1) or (2) above, the styrene (B) having a silicon-containing group has 4 or more and 6 or less silicon atoms in the silicon-containing group. Hard contact lens material.

[0054] (4) In the hard contact lens material according to any one of (1) to (3) above, the styrene (B) having a silicon-containing group contains tris (trimethylsiloxy) silylstyrene. Hard contact lens material.

[0055] (5) A hard contact lens comprising a polymer of the hard contact lens material according to any one of (1) to (4) above, or a processed product of the polymer. Hard contact lens.

[0056] (6) In the hard contact lens according to (5) above, the amount of bending deformation at the time of breakage of the hard contact lens is 70% or more. Hard contact lens.

[0057] (7) In the hard contact lens according to (5) or (6) above, the oxygen permeability coefficient of the hard contact lens is 120 × 10 －１１ (cm ２ / sec) · (mL O ２ / (mL × mmHg)) or more. Hard contact lens.

[0058] (8) A hard contact lens as described in any one of (5) to (7) above, wherein the durometer hardness (Type D) of the hard contact lens measured under a test environment of 23°C and 50% humidity is 74 or more and 78 or less. Of course, this is not limited to this.

[0059] As previously described, various embodiments of the present invention have been explained, but these are merely examples and do not limit the scope of the invention in any way. These novel embodiments can be implemented in various other forms, and various omissions, substitutions, and modifications can be made without departing from the spirit of the invention. These embodiments and their variations are included in the scope and spirit of the invention, as well as in the claims of the invention and its equivalents.

[0060] The hard contact lens material and hard contact lenses will be described in more detail below with reference to examples, but the document is not limited to these examples. 1. Components Used The names and abbreviations of the compounds used in the following examples and comparative examples are shown below.

[0061] 1-1. Substituted methacrylates (A) ・6F: 1,1,1,3,3,3-Hexafluoroisopropyl methacrylate [CAS: 3063-94-3, Molecular weight: 236, Ratio of fluorine atoms to carbon atoms: 0.857] ・5F: 2,2,3,3,3-Pentafluoropropyl methacrylate [CAS: 45115-53-5, Molecular weight: 218, Ratio of fluorine atoms to carbon atoms: 0.714] ・7F: 2,2,3,3,4,4,4-Heptafluorobutyl methacrylate [CAS: 13695-31-3, Molecular weight: 268, Ratio of fluorine atoms to carbon atoms: 0.875]

[0062] 1-2. Substituted Styrene (B) • TTMS: Tris(trimethylsiloxy)silylstyrene [CAS: 18547-54-1, Molecular Weight: 399]

[0063] 1-3. Methacryloyl group-containing silicone monomer (C)- TRIS: 3-methacryloxypropyltris(trimethylsiloxy)silane[CAS: 17096-07-0, molecular weight: 423, in the above general formula (I), Z is a direct bond, n is 3, R ２ , R ３ and R ４ are each a methyl group, and a is 3]- SiGMA: (3-methacryloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane [CAS: 69861-02-5, molecular weight: 423, in the above general formula (I), Z is the above linking structure (I-1), n is 3, R １ , R ２ , R ３ and R ４ are each a methyl group, and a is 2] - MP-TRIS: Methacryloxymethylphenethyltris(trimethylsiloxy)silane [CAS: 108587-59-3, molecular weight: 499, in the above general formula (I), Z is the above linking structure (I-2), n is 2, R ２ , R ３ and R ４ are each a methyl group, and a is 3]

[0064] 1-4. (Meth)acryloyl group-containing monomer (D) - M2D17 [CAS: 70877-62-2, molecular weight: 1672, in the above general formula (II), X is a methyl group, R ５ , R ６ , R ７ , R ８ , R ９ and R １０ are each a methyl group, n １ is 4, and n ２ (average value) is 17] - PDMS23 [CAS: 58130-03-3, molecular weight: 2088, in the above general formula (II), X is a methyl group, R ５ , R ６ , R ７ , R ８ , R ９ and R １０ are each a methyl group, n [[ID=5Compounds with an average value of 23: • PDMS37 [CAS: 58130-03-3, Molecular weight: 3124, In the above general formula (II), X is a methyl group, R ５ , R ６ , R ７ , R ８ , R ９ and R １０ These are methyl groups and n １ 3, n ２ Compounds with an average value of 37]

[0065] • M2D25 [CAS: 70877-62-2, Molecular weight: 2264, In the above general formula (II), X is a methyl group, R ５ , R ６ , R ７ , R ８ , R ９ and R １０ These are methyl groups and n １ 4, n ２ Compounds with an average value of 25: • P600-DMA [CAS: 25852-47-5, Molecular weight: 770, In the above general formula (III), X １ is a methyl group, n ３ Compounds with an average value of 14: P1000-DMA [CAS: 25852-47-5, Molecular weight: 1166, In the above general formula (III), X １ is a methyl group, n ３ Compounds with an average value of 23] ・1700B [CAS: 87003-89-2, Molecular weight: 1756, In the above general formula (IV), n ４ (Average value) is 7, n ５ Compounds with an average value of 17]

[0066] 1-5. Unsaturated double bond-containing hydrophilic monomer (E) ・MAA: Methacrylic acid [CAS: 79-41-4, Molecular weight: 86]

[0067] 1-6. Methacryloyl group-containing monomers (F) ・NPG-DMA: Neopentyl glycol dimethacrylate [CAS: 1985-51-9, Molecular weight: 240] ・EDMA: Ethylene glycol dimethacrylate [CAS: 97-90-5, Molecular weight: 198] ・DEGDMA: Diethylene glycol dimethacrylate [CAS: 2358-84-1, Molecular weight: 242] ・TEGDMA: Triethylene glycol dimethacrylate [CAS: 109-16-0, Molecular weight: 286] ・HDDMA: 1,6-Hexanediol dimethacrylate [CAS: 6606-59-3, Molecular weight: 254]

[0068] 1-7. Reactive monomer (G) ・RUVA-93:2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole [CAS: 96478-09-0, Molecular weight: 323]

[0069] 1-8. Polymerization Initiators (J) ・AIBN: 2,2'-Azobis(isobutyronitrile) [CAS: 78-67-1, Molecular weight: 164] ・Darocur1173: 2-Hydroxy-2-methylpropiophenone [CAS: 7473-98-5, Molecular weight: 164] ・PX431: 2,5-Dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane [CAS: 13052-09-0, Molecular weight: 431] ・V-65: 2,2'-Azobis(2,4-dimethylvaleronitrile) [CAS: 4419-11-8, Molecular weight: 248]

[0070] 1-9. Components (R) that do not fall under (A) to (H) and (J) above: ・3F: 2,2,2-trifluoroethyl methacrylate [CAS: 352-87-4, Molecular weight: 168, Ratio of fluorine atoms to the number of carbon atoms: 0.5] ・13F: 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate [CAS: 2144-53-8, Molecular weight: 432, Ratio of fluorine atoms to the number of carbon atoms: 1.08] ・PDMS07 [CAS: 58130-03-3, Molecular weight: 904, In the above general formula (II), X is a methyl group, R ５ , R ６ , R７ , R ８ , R ９ and R １０ These are methyl groups and n １ 3, n ２ Compounds with an average value of 7: ・M2D10 [CAS: 70877-62-2, Molecular weight: 1154, In the above general formula (II), X is a methyl group, R ５ , R ６ , R ７ , R ８ , R ９ and R １０ These are methyl groups and n １ 4, n ２ Compounds with an average value of 10: ・M2D50 [CAS: 70877-62-2, Molecular weight: 4114, In the above general formula (II), X is a methyl group, R ５ , R ６ , R ７ , R ８ , R ９ and R １０ These are methyl groups and n １ 4, n ２ Compounds with an average value of 50: PEG-DA [CAS: 26570-48-9, Molecular weight: 522, In the above general formula (III), X １ is a hydrogen atom, n ３ Compounds with an average value of 9]

[0071] • UDMA: Urethane dimethacrylate [CAS: 72869-86-4, Molecular weight: 471, Compound represented by the following formula] • NVP: N-vinyl-2-pyrrolidone [CAS: 88-12-0, Molecular weight: 111] • VBMA: 4-vinylbenzyl methacrylate [CAS: 99413-45-3, Molecular weight: 202]

[0072] 2. Preparation of homopolymers of (meth)acryloyl group-containing monomer (D) (Homopolymer 1) First, 10 g of PDMS23 and 0.06 g of Darocur1173 were placed in a 20 mL glass bottle and stirred at room temperature for about 18 hours. Next, this monomer mixture was poured into a mold (made of polypropylene) for producing a disc-shaped polymer with a final shape of 16 mm in diameter and 0.6 mm in thickness, and the upper and lower molds were assembled. After that, approximately 35 mW / cm² was applied. ２ The polymerization was completed by irradiating the material with ultraviolet light (wavelength between 300 nm and 400 nm) for 20 minutes. After polymerization, only the upper mold was removed, leaving the polymer contained in the lower mold. Next, the mold was placed in a heat treatment device and reheated according to the following schedule to obtain a disc-shaped polymer.

[0073]

[0074] (Homopolymers 2-11) Similarly, 10 g each of PDMS07, PDMS37, M2D10, M2D17, M2D25, M2D50, P600-DMA, P1000-DMA, 1700B, and PEG-DA, along with 0.06 g of Darocur1173, were weighed out, and disc-shaped polymers were prepared in the same manner as homopolymer 1.

[0075] 3. Preparation of homopolymers of methacryloyl group-containing monomers (F) (Homopolymers 12-17) 10 g each of NPG-DMA, EDMA, DEGDMA, TEGDMA, HDDMA, and UDMA, and 0.06 g of Darocur 1173 were weighed out, and disc-shaped polymers were prepared in the same manner as for homopolymer 1.

[0076] 4. Measurement of Glass Transition Temperature (Tg) First, from the disc-shaped polymers obtained above, test specimens of homopolymers 2 to 11 were extracted using a φ5 mm biopsy trephine. Homopolymers 12 to 17 were pulverized using a small pulverizer to obtain test specimens. Next, these test specimens were placed in an aluminum container used for differential scanning calorimetry and sealed. At this time, the mass of the test specimens was approximately 10 mg to 13 mg. Next, using an empty aluminum container as a reference material, the glass transition temperatures of homopolymers 2 to 11 were measured using a differential scanning calorimetry meter (NETZSCH, "DSC3500 Sirius") according to the schedule shown in Table 2, and the glass transition temperatures of homopolymers 12 to 17 according to the schedule shown in Table 3.

[0077]

[0078]

[0079] From the obtained DSC charts, the midpoint glass transition temperature was defined as the glass transition temperature of the homopolymer. As a result, the glass transition temperatures of each homopolymer were as shown in Tables 4 and 5 below.

[0080]

[0081]

[0082] 5. Preparation of hard contact lenses (Example 1) 6F, TTMS, TRIS, M2D17, MAA, NPG-DMA, RUVA-93, and AIBN were weighed into a 30 mL glass bottle in the following amounts and stirred at room temperature for approximately 18 hours. This prepared a monomer mixture (hard contact lens material).

[0083] • 6F: 6.7672g (36.08 mol%, 30.76 mass%) • TTMS: 1.6918g (5.34 mol%, 7.69 mass%) • TRIS: 8.4590g (25.19 mol%, 38.45 mass%) • M2D17: 1.7160g (1.29 mol%, 7.80 mass%) • MAA: 1.5400g (22.52 mol%, 7.00 mass%) • NPG-DMA: 1.6500g (8.64 mol%, 7.50 mass%) • RUVA-93: 0.1100g (0.43 mol%, 0.50 mass%) • AIBN: 0.0660g (0.51 mol%, 0.30 mass%)

[0084] Next, the monomer mixture was filled into a polyethylene container with an inner diameter of 13.0 mm, an outer diameter of 15.0 mm, and a length of 200 mm, and sealed with a polyethylene cap. Then, it was immersed in a water bath pre-set to 38.5°C and polymerized for 144 hours. After that, the cap was removed from the container, and the mixture was reheated under the conditions shown in Table 6 to obtain a rod-shaped polymer of the monomer mixture. From this polymer of the monomer mixture, a button shape with a diameter of 12.0 mm and a thickness of 5.0 mm was cut, and this button-shaped polymer was then cut and processed into a lens shape to obtain a hard contact lens.

[0085]

[0086] (Examples 2-5, Comparative Examples 1-4) Monomer mixtures (hard contact lens materials) and hard contact lenses were prepared in the same manner as in Example 1, except that the compositions were as shown in Table 7.

[0087] (Examples 6-9) Monomer mixtures (hard contact lens materials) and hard contact lenses were prepared in the same manner as in Example 1, except that the compositions were as shown in Table 8.

[0088] (Comparative Examples 5-7) A monomer mixture (hard contact lens material) was prepared in the same manner as in Example 1, except for the composition shown in Table 8, and degassed by freezing and thawing with liquid nitrogen. Next, the monomer mixture was placed in a polymerization container consisting of two Teflon® sheets separated by an elastomer and held together by a double clip. After filling, the container was purged with nitrogen gas and sealed tightly. This container was heated at 70°C for 4 hours, then at 80°C for 3 hours and at 110°C for 1 hour. The resulting sheet-like polymer of the monomer mixture was further heated at 120°C for 1 hour, and after cooling, a button shape with a diameter of 12.0 mm and a thickness of 5.0 mm was cut from this sheet. A hard contact lens was obtained by cutting this button-shaped polymer into a lens shape.

[0089] (Comparative Examples 8 and 9) A monomer mixture (hard contact lens material) was prepared in the same manner as in Example 1, except for the composition shown in Table 8. The mixture was placed in a borosilicate glass test tube with a diameter of 15.0 mm and a length of 150 mm and sealed tightly. This container was polymerized in a constant temperature water bath at 35°C for 40 hours. After that, the test tube was transferred to a circulating dryer and heated at 50°C for 6 hours, followed by a heating rate of 10°C per hour up to 130°C to heat polymerize the components and obtain a rod-shaped monomer mixture polymer. A button shape with a diameter of 12.0 mm and a thickness of 5.0 mm was cut from this polymer, and a hard contact lens was obtained by cutting this button-shaped polymer into a lens shape.

[0090] (Examples 10-17, Comparative Example 10) Monomer mixtures (hard contact lens materials) and hard contact lenses were prepared in the same manner as in Example 1, except that the compositions were as shown in Table 9.

[0091] (Examples 18, 19 and Comparative Examples 11, 12) Monomer mixtures (hard contact lens materials) and hard contact lenses were prepared in the same manner as in Example 1, except that the compositions were as shown in Table 10.

[0092] 6. Measurement and Evaluation The polymers of the monomer mixtures obtained in each example and comparative example, as well as the hard contact lenses, were evaluated for machinability, hardness, oxygen permeability coefficient, and compression bending properties.

[0093] 6-1. Evaluation of Machinability When hard contact lenses were processed by the lace-cutting method from a polymer of a monomer mixture in the shape of a button with a diameter of 12.0 mm and a thickness of 5.0 mm, the surface condition of the hard contact lenses after cutting and polishing was evaluated according to the following criteria. <Evaluation Criteria> G (Good): The surface of the hard contact lens after polishing had excellent transparency, and no lace marks were observed due to cutting. B (Bad): Due to the softness of the monomer mixture polymer, the cutting resistance was high, and the cutting surface and the subsequent polished surface became rough and white.

[0094] 6-2. Hardness Measurement Button-shaped test pieces with a diameter of 12.0 mm and a thickness of 5.0 mm were cut from the polymer of the monomer mixture and their surfaces were polished. Next, after conditioning for 96 hours in an environment of 23°C and 50%, the hardness of the test pieces was measured using a durometer (Type D) (GSD-720J-R, manufactured by Teclock Co., Ltd.). Three tests were performed, and the average value (rounded to the first decimal place) was taken as the hardness.

[0095] 6-3. Measurement of Oxygen Permeability Coefficient Flat test pieces with thicknesses of 0.14 mm, 0.18 mm, 0.25 mm, 0.32 mm, and 0.40 mm were cut from a button-shaped monomer mixture polymer with a diameter of 12.0 mm and a thickness of 5.0 mm, and their surfaces were polished. Next, the oxygen permeability coefficient was measured according to the measurement method by polarography described in ISO 18369-4:2017. An oxygen permeability analyzer (Createch Rehder Development Company, "201T") was used for the measurement.

[0096] 6-4. Compression Bending Test (Calculation of Bending Deformation at Breakdown) A hard contact lens with the following shape was fabricated from a polymer of a button-shaped monomer mixture with a diameter of 12.0 mm and a thickness of 5.0 mm: Front: Single cut (radius of curvature 8.00 mm ± 0.025 mm) Back: Single cut (radius of curvature 7.80 mm ± 0.025 mm) Total diameter: 9.5 mm ± 0.1 mm Center thickness: 0.20 mm ± 0.01 mm Edge thickness: 0.24 mm ± 0.01 mm (edge ​​shape is rounded) Maximum prism error: 0.5 cm / m Next, this hard contact lens was tested according to the method described in ISO 18369-4:2017 to determine the bending deformation at breakdown. The number of tests was set to 5, and the average value (rounded to two decimal places) was taken as the bending deformation at breakdown.

[0097] These results are shown in Tables 7 to 10 below.

[0098] In Table 7, the composition units are shown in mole percent in the upper row and mass percent in the lower row (in parentheses). As shown in Table 7, the hard contact lenses of Examples 1 to 5 have good processability and an oxygen permeability coefficient of 130 × 10 －１１ (cm ２ / sec)・(mLO ２ / (mL × mmHg)) 156 × 10 －１１ (cm ２ / sec)・(mLO ２ For values ​​of (mL × mmHg) or less, the bending deformation was between 75.0% and 83.0%. In contrast, the hard contact lenses of Comparative Examples 1 to 3 were made from monomer mixtures using monomers (PDMS07, M2D50, or PEG-DA) that deviated from the molecular structure range of (meth)acryloyl group-containing monomer (D). As a result, the bending deformation of the hard contact lenses of Comparative Examples 1 and 3 was small, at 68.4% and 67.1%, respectively. Furthermore, the polymer of the monomer mixture in Comparative Example 2 was soft, making it difficult to cut and polish into a lens shape, and therefore unsuitable for hard contact lenses.

[0099] The hard contact lens of Comparative Example 4 was made from a monomer mixture using two types of crosslinkable monomers (NPG-DMA and UDMA) without using (meth)acryloyl group-containing monomer (D). As a result, the bending deformation of the hard contact lens of Comparative Example 4 was small, at 66.9%. Thus, the hard contact lenses of Examples 1 to 5, obtained using a monomer mixture containing (meth)acryloyl group-containing monomer (D) in a molar ratio of (meth)acryloyl group-containing monomer (D) to methacryloyl group-containing monomer (F) in the range of 0.12 to 0.2, have high oxygen permeability and bending deformation. Therefore, it is considered that they are stronger against bending deformation and less prone to breakage than conventional hard contact lenses while maintaining excellent oxygen permeability.

[0100]

[0101] In Table 8, the composition units are shown in mole percent in the upper row and mass percent in the lower row (in parentheses). As shown in Table 8, the hard contact lenses of Examples 6 to 9 have good processability and an oxygen permeability coefficient of 131 × 10⁻¹⁰. －１１ (cm ２ / sec)・(mLO ２ / (mL × mmHg)) 183 × 10 －１１ (cm ２ / sec)・(mLO ２ For values ​​of (mL × mmHg) or less, the bending deformation was between 73.1% and 82.0%. In contrast, the hard contact lens of Comparative Example 5 was made using a monomer (M2D50) that deviated from the molecular structure range of the (meth)acryloyl group-containing monomer (D), and using a monomer mixture in which the molar ratio of monomer (M2D50) to methacryloyl group-containing monomer (F) was less than 0.12. As a result, the bending deformation of the hard contact lens of Comparative Example 5 was small at 63.3%.

[0102] The hard contact lens of Comparative Example 6 used a (meth)acryloyl group-containing monomer (D), but was manufactured using a monomer mixture in which the molar ratio of (meth)acryloyl group-containing monomer (D) to methacryloyl group-containing monomer (F) was less than 0.12. As a result, the bending deformation of the hard contact lens of Comparative Example 6 was small, at 58.4%. The hard contact lens of Comparative Example 7 used a monomer (M2D10) that deviates from the molecular structural range of (meth)acryloyl group-containing monomer (D), and was manufactured using a monomer mixture in which the molar ratio of monomer (M2D10) to methacryloyl group-containing monomer (F) was greater than 0.2. As a result, the bending deformation of the hard contact lens of Comparative Example 7 was small, at 53.9%.

[0103] The hard contact lenses of Comparative Examples 8 and 9 were made from contact lens material that did not contain (meth)acryloyl group-containing monomer (D). As a result, the bending deformation of the hard contact lenses of Comparative Examples 8 and 9 was low, at 58.9% and 65.6%, respectively. Thus, the hard contact lenses of Examples 6 to 9, obtained using a monomer mixture containing (meth)acryloyl group-containing monomer (D) in a molar ratio of (meth)acryloyl group-containing monomer (D) to methacryloyl group-containing monomer (F) in the range of 0.12 to 0.2, have high oxygen permeability and bending deformation. Therefore, it is considered that they are stronger against bending deformation and less prone to breakage than conventional hard contact lenses, while maintaining excellent oxygen permeability.

[0104]

[0105] In Table 9, the upper row of the composition units represents mole percent, and the lower row in parentheses represents mass percent. As shown in Table 9, the hard contact lenses of Examples 10 to 17 have good processability and an oxygen permeability coefficient of 158 × 10⁻⁶. －１１ (cm ２ / sec)・(mLO ２ / (mL × mmHg)) 198 × 10 －１１ (cm ２ / sec)・(mLO ２For values ​​of (mL × mmHg) or less, the bending deformation was between 77.0% and 82.8%. Thus, the hard contact lenses of Examples 10 to 17, obtained using a monomer mixture containing (meth)acryloyl group-containing monomer (D) and a molar ratio of (meth)acryloyl group-containing monomer (D) to methacryloyl group-containing monomer (F) in the range of 0.12 to 0.2, have high oxygen permeability and bending deformation. Therefore, it is considered that they maintain excellent oxygen permeability while being more resistant to bending deformation and less prone to breakage than conventional hard contact lenses.

[0106] In contrast, the hard contact lens of Comparative Example 10 was manufactured using a monomer mixture in which the amount of (meth)acryloyl group-containing monomer (D) used exceeded 1.6 mol%, and the molar ratio of (meth)acryloyl group-containing monomer (D) to methacryloyl group-containing monomer (F) also exceeded 0.2. As a result, the polymer of the monomer mixture of Comparative Example 10 was soft, making it difficult to cut and polish into a lens shape, and therefore unsuitable for hard contact lenses.

[0107]

[0108] In Table 10, the upper row of the composition units represents mole percent, and the lower row in parentheses represents mass percent. As shown in Table 10, the hard contact lenses of Examples 18 and 19 have good processability and an oxygen permeability of 131 × 10⁻¹⁰. －１１ (cm ２ / sec)・(mLO ２ / (mL × mmHg)) and 149 × 10 －１１ (cm ２ / sec)・(mLO ２The bending deformation amounts were 77.8% and 80.6% (mL × mmHg). The hard contact lenses of Examples 18 and 19, and the hard contact lens of Example 2, which has a similar composition, were made using substituted methacrylate (A) having a molecular structure in which the ratio of fluorine atoms to carbon atoms is 0.6 or more and 0.9 or less. Since all of these hard contact lenses have high oxygen permeability and bending deformation, it is considered that they are stronger against bending deformation and less prone to breakage than conventional hard contact lenses while maintaining excellent oxygen permeability.

[0109] In contrast, the hard contact lens of Comparative Example 11 was manufactured using a substituted methacrylate (A) having a molecular structure in which the ratio of fluorine atoms to carbon atoms is less than 0.6 (specifically 0.5). Therefore, the oxygen permeability coefficient of the hard contact lens of Comparative Example 11 was 83 × 10⁻¹⁰. －１１ (cm ２ / sec)・(mLO ２ The humidity was low (mL × mmHg). Furthermore, the hard contact lens of Comparative Example 12 was made using substituted methacrylate (A) having a molecular structure in which the ratio of fluorine atoms to carbon atoms was greater than 0.9 (specifically 1.08). As a result, the hard contact lens material of Comparative Example 12 was soft and sticky and could not be removed from the polyethylene container used for polymerization.

[0110] Furthermore, if you use another substituted styrene (B) (styrene (B) having a silicon-containing group) instead of tris(trimethylsiloxy)silylstyrene and prepare a monomer mixture (hard contact lens material) and manufacture a hard contact lens in the same manner as in the above example, and then measure and evaluate it in the same manner as above, you will get the same effects as in the above example.

[0111] 1: Hard contact lens placement jig, 2: Hard contact lens, d: Initial diameter, D Ｔ : Distance between installation fixtures

Claims

1. A hard contact lens material comprising: 35 mol% or more and 55 mol% or less of a fluoroalkyl methacrylate (A) having a molecular structure in which the ratio of the number of fluorine atoms to the number of carbon atoms is 0.6 or more and 0.9 or less; 4 mol% or more and 15 mol% or less of a styrene (B) having a silicon-containing group; and 10 mol% or more and 30 mol% or less of at least one silicone monomer (C) having a methacryloyl group represented by the following general formula (I). [Z is one selected from a direct bond, the following linking structure (I-1), and the following linking structure (I-2), and R ５ , ３ , , ４ , ２ , , １ , １ , R ２ , R ３ and R ４ are each independently an alkyl group having 1 to 4 carbon atoms, a is an integer of 1 to 3, and n is 2 or 3.] The glass transition temperature of the homopolymer is -30°C or lower, and at least one selected from monomers (D) having two (meth)acryloyl groups in the molecular structures represented by the following general formulas (II) to (IV) is 0.6 mol% or more and 1.6 mol% or less. [In the formula, X is a methyl group or a hydrogen atom, and R ５ , R ６ , R ７ , R ８ , R ９ and R １０ are each independently an alkyl group having 1 to 6 carbon atoms, n １ is 3 or 4, and n ２ is an integer of 12 or more and 40 or less.] [In the formula, X １ is a methyl group or a hydrogen atom, and n ３ is an integer of 12 or more and 30 or less.] [In the formula, n ４ is an integer of 4 or more and 15 or less, and n ５ [where is an integer between 6 and 20.] A hard contact lens material comprising 18 mol% to 25 mol% of a hydrophilic monomer (E) having one unsaturated double bond in its molecular structure, and a monomer (F) having a homopolymer glass transition temperature of 190°C or higher and two methacryloyl groups in its molecular structure, wherein the molar ratio of monomer (D) to monomer (F) is 0.12 to 0.

2.

2. A hard contact lens material according to claim 1, wherein the fluoroalkyl methacrylate (A) comprises 1,1,1,3,3,3-hexafluoroisopropyl methacrylate.

3. A hard contact lens material according to claim 1 or claim 2, wherein the styrene (B) having a silicon-containing group has 4 or more silicon atoms in the silicon-containing group and 6 or less.

4. A hard contact lens material according to any one of claims 1 to 3, wherein the silicon-containing styrene (B) comprises tris(trimethylsiloxy)silylstyrene.

5. A hard contact lens comprising a polymer of the hard contact lens material described in any one of claims 1 to 4, or a processed product of the polymer.

6. A hard contact lens according to claim 5, wherein the amount of bending deformation of the hard contact lens at the time of breakage is 70% or more.

7. In the hard contact lens according to claim 5 or claim 6, the oxygen permeability coefficient of the hard contact lens is 120 × 10 －１１ (cm ２ / sec)・(mLO ２ Hard contact lenses with a pressure of 1 / (mL × mmHg) or higher.

8. A hard contact lens according to any one of claims 5 to 7, wherein the durometer hardness (Type D) of the hard contact lens measured under a test environment of 23°C and 50% humidity is 74 or more and 78 or less.

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